Methods and systems for coating articles having a plastic substrate

ABSTRACT

Methods for coating articles that include a plastic substrate are disclosed. Certain methods include the steps of (i) applying a composition that includes an adhesion promoting agent to at least a portion of the substrate by a first application technique, (ii) applying a composition that includes an adhesion promoting agent over at least a portion of the composition applied in step (i) by a second application technique that is different from the first application technique, and (iii) applying a protective and decorative coating system over at least a portion of the compositions applied in steps (i) and (ii). Systems for coating articles that include a plastic substrate are also disclosed.

FIELD OF THE INVENTION

The present invention relates to methods and systems for coatingarticles having a plastic substrate, such as certain interior andexterior parts on automobiles. More particularly, the methods andsystems of the present invention involve the application of compositionsthat include an adhesion promoting agent to such articles.

BACKGROUND OF THE INVENTION

Plastics are used in a wide variety of molding applications for thepreparation of molded articles for use in the automotive, industrial andappliance markets, among others. Vehicles, for example, include manyinterior and exterior parts and attachments that are constructed fromplastics, such as mirror casings, fenders, bumper covers, spoilers,dashboards, interior trim, etc. The preparation of such articlesgenerally includes the steps of molding an article from a polyolefin orother resin and applying to the molded article one or more film-formingcoating layers to protect and/or color the article.

One of the difficulties associated with the use of plastic substrates isthat typical film-forming compositions used for protective anddecorative coatings do not adhere well to such substrates. A solution tothis problem is to include a layer of a composition that includes anadhesion promoting material, such as a chlorinated polyolefin (“CPO”),between the substrate and the film-forming coating.

In refinishing molded articles constructed from plastics, for example,the need to include a layer of a composition that includes an adhesionpromoting material can make the refinishing process complex,time-consuming, and expensive. Historically, the refinishing of sucharticles, such as automobile parts, has involved several steps. First,the surface to be refinished is cleaned, such as with a detergent, andallowed to dry. Second, the surface is wiped with a solvent, such as analcohol. Third, the surface is scuffed, often using sandpaper or anabrasive pad to promote mechanical adhesion of subsequent materials. Thescuffing step sometimes includes the addition of a sanding paste.Fourth, the surface is rinsed with water and allowed to dry. Fifth, thesurface is wiped with a solvent to, for example, remove dust, oil,fingerprints, etc. Sixth, the surface is wiped or sprayed with acomposition containing an antistatic agent, which is then flashed toremove solvents from the composition. Next, a material containing a CPOis sprayed onto the surface and then flashed to remove solvents from thematerial. Finally, a protective and decorative coating system is appliedto the surface and cured.

As is apparent, such refinishing processes are complex, can generate asignificant amount of waste, and can be very labor intensive andtime-consuming. Moreover, because a CPO is applied in only one step,usually by spray application, such processes can sometimes result ininconsistent adhesion results, particularly in an automobile body shopsetting, because there is a significant possibility that a portion ofthe surface to be refinished is not covered by a sufficient amount ofadhesion promoting material.

As a result, there is a need for improved methods and systems forcoating articles having a plastic substrate.

SUMMARY OF THE INVENTION

In one respect, the present invention is directed to methods of coatingarticles comprising a plastic substrate. In certain embodiments, themethods comprise the steps of (a) applying a composition comprising anadhesion promoting agent to at least a portion of the substrate by afirst application technique; (b) applying a composition comprising anadhesion promoting agent over at least a portion of the compositionapplied is step (a) by a second application technique that is differentfrom the first application technique; and (c) applying a protective anddecorative coating system over at least a portion of the compositionsapplied is steps (a) and (b).

In other embodiments, the methods for coating an article comprising aplastic substrate comprise the steps of (a) applying a compositioncomprising an adhesion promoting agent to at least a portion of aplastic substrate by a first application technique; and (b) applying aprotective and decorative coating system over at least a portion of thecomposition applied in step (a), wherein the protective and decorativecoating system comprises a coating layer deposited from a coatingcomposition that comprises an (i) adhesion promoting agent comprising ahalogenated polyolefin, and (ii) a resin that is compatible with theadhesion promoting agent, wherein the coating layer is deposited by anapplication technique that is the same as or different from the firstapplication technique.

In yet other embodiments, the methods of the present invention comprisethe steps of (a) applying a first composition comprising an adhesionpromoting agent to at least a portion of the substrate; (b) applying asecond composition comprising an adhesion promoting agent over at leasta portion of the composition applied in step (a); and (c) applying aprotective and decorative coating system over at least a portion of thecompositions applied in steps (a) and (b), wherein the first and secondcompositions are different and wherein at least one of the first andsecond compositions is applied to the substrate by wiping or wherein oneof the compositions comprising an adhesion promoting agent is applied bywiping and the other is applied by spraying.

In another respect, the present invention is directed to systems forcoating articles having a plastic substrate. These systems of thepresent invention comprise: (a) means for applying a compositioncomprising an adhesion promoting agent to at least a portion of thesubstrate by a first application technique; (b) means for applying acomposition comprising an adhesion promoting agent to the substrate by asecond application technique that is different from the firstapplication technique; and (c) means for applying a protective anddecorative coating system to at least a portion of the substrate. Insome embodiments, certain elements of these systems may be provided inthe form of a kit.

DETAILED DESCRIPTION OF EMBODIMENTS OF THE INVENTION

For purposes of the following detailed description, it is to beunderstood that the invention may assume various alternative variationsand step sequences, except where expressly specified to the contrary. Itis also to be understood that the specific devices and processesdescribed in the following specification are simply exemplaryembodiments of the invention. Hence, any specific dimensions or otherphysical characteristics related to the embodiments disclosed herein arenot to be considered as limiting. Moreover, other than in any operatingexamples, or where otherwise indicated, all numbers expressing, forexample, quantities of ingredients used in the specification and claimsare to be understood as being modified in all instances by the term“about”. Accordingly, unless indicated to the contrary, the numericalparameters set forth in the following specification and attached claimsare approximations that may vary depending upon the desired propertiesto be obtained by the present invention. At the very least, and not asan attempt to limit the application of the doctrine of equivalents tothe scope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between (andincluding) the recited minimum value of 1 and the recited maximum valueof 10, that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10.

The present invention is directed to methods and systems for coatingarticles comprising a plastic substrate, such as certain interior andexterior parts on automobiles. In certain embodiments, the methods ofthe present invention comprise the steps of (a) applying a compositioncomprising an adhesion promoting agent to at least a portion of thesubstrate by a first application technique; (b) applying a compositioncomprising an adhesion promoting agent over at least a portion of thecomposition applied in step (a) by a second application technique thatis different from the first application technique; and (c) applying aprotective and decorative coating system over at least a portion of thecompositions applied in steps (a) and (b).

As indicated, the methods and systems of the present invention aredirected to coating articles comprising a plastic substrate. In certainembodiments, such coating methods and systems are directed to therefinishing of such articles. As used herein, the term “refinish” refersto the act of redoing, restoring or repairing the surface or finish ofan article or, in the case of automobile repairs, for example, thepreparation of the surface or finish of a unused article in connectionwith such a repair. As used herein, the term “plastic substrate” refersto a substrate having, on at least a portion of its surface, a plastic.As used herein, the term “plastic” is intended to include anythermoplastic or thermosetting synthetic nonconductive material used ininjection or reaction molding, sheet molding or other similar processeswhereby parts are formed, such as, for example, acrylonitrile butadienestyrene (“ABS”), thermoplastic polyolefin (“TPO”), polycarbonate,thermoplastic elastomer, polyester thermoset, polyurethane,thermoplastic polyurethane, sheet molded compound, fiberglass reinforcedpolyester, among others. As used herein, the term “olefin” and liketerms refers to unsaturated aliphatic hydrocarbons having one or moredouble bonds, such as those obtained by cracking petroleum fractions.Specific examples of olefins include, but are not limited to, propylene,1-butene, 1,3-butadiene, isobutylene and diisobutylene. As used herein,the term “polyolefin” and like terms refers to a polymer formed fromolefins. Common examples are polypropylene and polybutylene and includethe class of TPOs. As used herein, the term “polymer” refers tooligomers and both homopolymers and copolymers.

In certain embodiments, the methods of the present invention comprisethe step of applying a composition comprising an adhesion promotingagent to at least a portion of the substrate by a first applicationtechnique. As used herein, the term “adhesion promoting agent” includesany adhesion promoting or adhesion improving material known to those ofskill in the art of formulating materials for coating plastic articles.Examples of such materials include, without limitation, halogenatedpolyolefin polymers, such as CPOs or polyolefins that include one ormore other halogen atoms, such as fluorine, chlorine, bromine, oriodine.

CPO resins, for example, can be produced by ionic polymerization orZiegler-Natta polymerization according to well-known techniques, such asthat reviewed in Billmeyer, “Textbook of Polymer Science,” p. 311-325,Wiley-Interscience, New York, N.Y., 1962. Polyolefin resins that can beused to produce CPO resins include, for example, polyethylene,polypropylene, polybutylene, polyisoprene, polybutadiene and mixturesthereof.

The crystallinity of the polyolefin can be adjusted by choosing aspecific stereoisomer of the polymer. Isotactic polymers (in which allside groups are arranged on one side of the polymer backbone),syndiotactic polymers (in which side groups are arranged alternatelyabove and below the plane of the polymer backbone), or atactic polymers(in which side groups are arranged randomly about the plane of thepolymer backbone) can be used to prepare CPOs. In addition, thecrystallinity of the polyolefin can also be adjusted by varying theamount of chlorine in the backbone. Generally, as the chlorine contentrises, the crystallinity of the polymer decreases and the solubility ofthe polymer in various solvents, including water, increases.

A solvent is sometimes used in preparing a polyolefin resin. Suitablesolvents include, for example, aliphatic hydrocarbons such as hexane orheptane; aromatic hydrocarbons such as cyclohexane, toluene, or xylene;alcohols such as isopropanol, butanol, 2-ethylhexanol or propyleneglycol; ethers such as the monoethyl, monobutyl or monohexyl esters ofethylene glycol or diethylene glycol; esters such as butyl acetate,ethyl acetate, 2-ethylhexyl acetate, or ethyl-3-ethoxy propionate; andketones such as isophorone, 4-methoxy-pentanone, diisobutyl ketone, ormethyl isobutyl ketone; and the like.

Polyolefin resins can be chlorinated by solution, melt or solid polymerchlorination at moderate to high temperatures according to well-knowntechniques as reviewed, for example, in Raff and Doak, “CrystallineOlefin Polymers II,” p. 239-260, Interscience Publishers, New York,N.Y., 1964. For example, a suitable CPO resin can be prepared bybubbling chlorine gas through a hot solution of polyolefin in benzylchloride, or by irradiating a solution of polyolefin in carbontetrachloride with ultraviolet light.

As will be appreciated by the skilled artisan, CPO resins can beunstable and dechlorinate upon irradiation or exposure to elevatedtemperatures. Consequently, the exact chlorine level of a CPO resin canvary over time or from batch to batch. In certain embodiments of thepresent invention, the CPO resins used to prepare the compositionapplied by the first application technique may contain from about 0.50percent to about 70 percent chlorine, the percentages based on theweight of polyolefinic material present. In certain embodiments, thechlorine content is from about 10 percent to about 50 percent, or, insome embodiments, from about 20 percent to about 35 percent by weight.In certain embodiments, the chlorine is randomly present on thepolyolefinic backbone.

The dechlorination reaction that CPO resins are subjected to produceshydrochloric acid that may, if desired, be removed by a scavenger.Examples of materials which can be used as scavengers include organicmetal compounds such as dibutyl tin dilaurate, stannous octoate ordibutyl tin oxide; or epoxy resins such as epoxidized linseed oil, orpolyglycidyl ethers of polyphenols such as, for example, BISPHENOL A,which is commercially available from Shell Corporation.

CPOs suitable for use in the composition applied by the firstapplication technique in certain methods of the present invention may,in certain embodiments, have a weight average molecular weight rangingfrom about 10,000 to about 150,000, such as about 20,000 to about125,000, such as about 25,000 to about 105,000, as determined by gelpermeation chromatography using a polystyrene standard. Examples ofsuitable CPOs are disclosed in U.S. Pat. Nos. 6,593,423; 4,997,882;5,319,032; and 5,397,602, herein incorporated by reference. SuitableCPOs for use in the methods and systems of the present invention includematerials commercially available from Eastman Chemical Products, Inc.,of Rochester, N.Y. For example, CPOs available from Eastman Chemicalsunder the names CP153-2, CP164-1, CP343-1, CP343-3 and CP515-2 may beused. In addition, the Hardlen® CPO adhesion promoters available fromToyo Kasai Kogyo Co., Ltd., of Osaka, Japan may be used.

In certain embodiments, the composition applied by the first applicationtechnique in certain methods of the present invention comprises ahalogenated polyolefin that is modified by grafting a compatibilizingmaterial onto the polyolefin. For example, the composition applied bythe first application technique in certain methods of the presentinvention may comprise a CPO, such as those described earlier, with anacrylic monomer grafted thereon. In other embodiments, the compositionapplied by the first application technique may comprise an epoxy orpolyester modified CPO, among others. As used herein, the term“compatibilizing material” refers to moieties that modify a halogenatedpolyolefin so as to render the halogenated polyolefin compatible withother resin(s) that may be present in the composition. By “compatible”it is meant herein that the halogenated polyolefin and such other resinsdo not separate from each other in the composition. As will beunderstood by those skilled in the art, the specific chemistry of thecompatibilizing material may depend on the chemistry of the compositioninto which the halogenated polyolefin is sought to be added. It shouldbe understood, however, that even where the composition applied by thefirst application technique comprises a halogenated polyolefin that ismodified by grafting a compatibilizing material onto the polyolefin,other resins need not necessarily be present in the composition.

As mentioned earlier, in certain methods of the present invention, thecomposition applied by the first application technique comprises a CPOhaving an acrylic monomer grafted thereon. Particular examples ofacrylic monomers that may be grafted onto a halogenated polyolefin toproduce a modified halogenated polyolefin suitable for use in thepresent invention include, without limitation, acrylic acid, methacrylicacid, and esters thereof, such as acrylates and methacrylates. Usefulesters of acrylic or methacrylic acid include straight chain or branchedalkyl or hydroxyalkyl esters of acrylic or methacrylic acid. Usefulalkyl esters can contain about 1 to about 24 carbon atoms, andpreferably contain about 1 to about 18 carbon atoms. Non-limitingexamples of alkyl esters include methyl (meth)acrylate, ethyl(meth)acrylates, propyl (meth)acrylates, butyl (meth)acrylates, pentyl(meth)acrylates, hexyl (meth)acrylates, heptyl (meth)acrylates, octyl(meth)acrylates, nonyl (meth)acrylates, decyl (meth)acrylates, dodecyl(meth)acrylates, tetradecyl (meth)acrylates, hexadecyl (meth)acrylates,ethylhexyl (meth)acrylates, lauryl (meth)acrylates, stearyl(meth)acrylates and 2-ethylhexyl (meth)acrylate. Suitable hydroxyalkylesters include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl(meth)acrylate, 3-hydroxypropyl (meth)acrylate and hydroxybutyl(meth)acrylate. As used herein, “(meth)acrylate” and terms derivedtherefrom are intended to include both acrylate and methacrylate.

In certain embodiments, modified halogenated polyolefins suitable foruse in the methods and systems of the present invention may be producedby an atom transfer radical polymerization process (ATRP), such as isdescribed in U.S. Pat. No. 6,576,722 at col. 3, line 61 to col. 10, line17, which is incorporated herein by reference.

In certain embodiments, modified halogenated polyolefins suitable foruse in the methods and systems of the present invention may be producedby conventional free radical polymerization methods that will beunderstood by those skilled in the art. See Kirk-Othmer Encyclopedia ofChemical Technology, Vol. 1 (1963). As will be understood by the skilledartisan, such radical polymerization is typically conducted in asolution of organic solvent(s). For example, aromatic solvents, such astoluene, xylene and SOLVESSO 100 may be used. Moreover, conventionalradical reaction initiators may be used, such as peroxides, includingbenzoyl peroxide, lauroyl peroxide, t-butyl hydroperoxide, andt-butylperoxy-2-ethylhexanoate; and azo compounds, includingazobisvaleronitrile, azobisisobutylronitrile andazobis(2-methylpropionitrile).

It will be appreciated by the skilled artisan that the compoundsproduced by a conventional free radical polymerization process willtypically comprise a mixture of polymers. For example, when grafting anacrylic monomer onto a CPO by conventional free radical polymerization,the random nature of standard radical polymerization will likely producea resin composition comprising a mixture of non-graft CPO chains,acrylic polymers, and CPOs having an acrylic monomer grafted thereon.Nevertheless, such a polymerization will produce at least some of themodified halogenated polyolefins that may be used in the methods andsystems of the present invention. Thus, in certain embodiments, theadhesion promoting agent comprises a mixture of a halogenatedpolyolefin, an acrylic polymer, and a modified halogenated polyolefin.In these embodiments, the modified halogenated polyolefin may, forexample, comprise 1 to 50 percent by weight based on the total weight ofthe adhesion promoting agent. In such embodiments, the amount ofmodified halogenated polyolefin that may be present in the adhesionpromoting agent can range between any combination of the recited values,inclusive of the recited values.

In certain embodiments, the adhesion promoting agent comprises 1 to 10percent by weight or, in some embodiments, 1 to 5 percent by weight, or,in yet other embodiments, 1 to 2 percent by weight of the compositionapplied by the first application technique in certain methods of thepresent invention based on the total weight of the composition. In suchembodiments, the amount of adhesion promoting agent present in thecomposition applied by the first application technique can range betweenany combination of the recited values, inclusive of the recited values.

In addition to the adhesion promoting agent, the composition applied bythe first application technique in certain methods of the presentinvention may also comprise a solvent. In certain embodiments, thecomposition applied by the first application technique comprises asolvent that is an organic solvent or a mixture of organic solvent andan aqueous medium. Suitable organic solvents include, withoutlimitation, xylene, toluene, Aromatic 100 solvent, which is commerciallyavailable from Cumberland Products, Inc., Hodgenville, Ky., andalcohols, such as ethyl alcohol, propyl alcohol and diacetone alcohol,including mixtures thereof.

In certain embodiments, the organic solvent comprises 80 to 99 percentby weight or, in some embodiments 95 to 99 percent by weight, or, in yetother embodiments 98 to 99 percent by weight of the composition appliedby the first application technique in certain methods of the presentinvention based on the total weight of the composition. In suchembodiments, the amount of organic solvent that may be present in thecomposition applied by the first application technique can range betweenany combination of the recited values, inclusive of the recited values.

In certain embodiments, the composition applied by the first applicationtechnique may also comprise one or more antistatic agents, such asethoxylated amines, alkanolamides, quaternary ammonium compounds, andmixtures thereof. Specific examples include quaternary ammoniumethosulphate, such as Catafor™ CA 80, commercially available from AcetoCorporation, Lake Success, N.Y., and the LAROSTAT® line of antistaticadditives commercially available from BASF Corporation.

In certain embodiments, the antistatic agent comprises 0.1 to 5.0percent by weight or, in some embodiments 0.5 to 2.0 percent by weight,or, in yet other embodiments 1 to 2 percent by weight of the compositionapplied by the first application technique in certain methods of thepresent invention based on the total weight of the composition. In suchembodiments, the amount of antistatic agent present in the compositionapplied by the first application technique can range between anycombination of the recited values, inclusive of the recited values.

In certain embodiments, the solvent included in the composition appliedby the first application technique in certain methods of the presentinvention comprises an aqueous medium. In these embodiments, thecomposition applied by the first application technique may comprise anemulsion wherein the adhesion promoting agent and any organic solventthat may be present in the composition are dispersed in a continuousphase that comprises an aqueous medium.

As will be appreciated by those skilled in the art, in such emulsions,the intended ingredients of the dispersion, including the adhesionpromoting agent, can be dispersed in the aqueous medium with adispersing means such as a homogenizer. In these embodiments, theadhesion promoting agent may be adapted to a form that will admit it tothe dispersing means. For example, the adhesion promoting agent may bein the form of a solution or is dissolved with an organic solvent or amixture of organic solvents to make up an organic component that isintroduced into an aqueous medium in the presence of a stabilizer. Theresultant mixture can be described as an emulsion.

The stabilizer can be a surfactant, such as an anionic, cationic and/ora nonionic surfactant, or a mixture thereof. Suitable surfactantsinclude those that are described in the Kirk Othmer Encyclopedia ofChemical Technology, Third Edition, Volume 22, pages 332 to 432.Suitable anionic surfactants include carboxylic acids and their salts,sulfonic acids and their salts, sulfuric acid esters and their salts,phosphoric and polyphosphoric acid esters and their salts; suitablenonionic surfactants include ethoxylated alcohols, ethoxylatedalkylphenols, ethoxylated carboxylic esters, ethoxylated carboxylicamides, and fluorosurfactants; and suitable cationic surfactants includeoxygen-free amines, oxygen-containing amines, amide-linked amines, andquaternary ammonium salts.

In certain embodiments, the composition applied by the first applicationtechnique in certain methods of the present invention comprises 0.1 to20.0 percent by weight or, in some embodiments 0.1 to 10.0 percent byweight, or, in yet other embodiments, 0.1 to 2.0 percent by weight ofstabilizer based on the total weight of the material. In suchembodiments, the amount of stabilizer present in the composition appliedby the first application technique can range between any combination ofthe recited values, inclusive of the recited values.

As mentioned earlier, the intended ingredients of the dispersion,including the adhesion promoting agent, can be dispersed in the aqueousmedium with a dispersing means such as a homogenizer. In certainembodiments, the emulsion is particulated by subjecting it to stress bythe dispersing means. The mixture is subjected to stress sufficient toproduce microparticles which have a mean particle size diameter of, forexample, about 0.01 to 10 micrometers, such as about 0.05 to 0.3micrometers. Particle size can be measured with a particle size analyzersuch as the Coulter N4 instrument commercially available from Coulter,as will be understood by those skilled in the art.

One mode of subjecting the mixture to the appropriate stress is by theuse of a MICROFLUIDIZER® emulsifier that is available from MicrofluidicsCorporation in Newton, Mass. This emulsifier is described in U.S. Pat.No. 4,533,254, which is incorporated herein by reference. The deviceconsists of a high pressure (up to 20,000 pounds per square inch “psi”)pump and an interaction chamber wherein the emulsification takes place.The pump forces the mixture of ingredients in an aqueous medium into thechamber where it is split into at least two streams which pass at veryhigh velocity through at least two splits and collide resulting in theparticulation of the mixture into small particles. Generally, themixture is passed through the emulsifier once at a pressure between5,000 and 15,000 psi. Multiple passes can result in smaller averageparticle size and a narrower range for the particle size distribution.When using the aforesaid MICROFLUIDIZER® emulsifier, stress is appliedby liquid impingement as has been described. However, it should beunderstood that, if desired, other modes of applying stress to thepre-emulsification mixture can be utilized, such as the use ofultrasonic energy.

Stress is described as a force per unit area. Although the precisemechanism by which the MICROFLUIDIZER® emulsifier stresses thepre-emulsification mixture to particulates is not thoroughly understood,it is theorized that stress is exerted in more than one manner. It isbelieved that one manner in which stress is exerted is by shear. “Shear”means that the force is such that one layer or plane moves parallel toan adjacent parallel plane. Stress can also be exerted from all sides asa bulk compression stress. In this instance, stress could be exertedwithout any shear. A further manner of producing intense stress is bycavitation. Cavitation occurs when the pressure within a liquid isreduced enough to cause vaporization. The formation and collapse of thevapor bubbles occurs violently over a short time period and producesintense stress. Although not intending to be bound by theory, it isbelieved that both shear and cavitation contribute to producing thestress which particulates the mixture.

In certain embodiments, the aqueous medium comprises 60 to 99 percent byweight or, in some embodiments 75 to 95 percent by weight, or, in yetother embodiments 90 to 98 percent by weight of the composition appliedby the first application technique in certain methods of the presentinvention based on the total weight of the material. In suchembodiments, the amount of aqueous medium present in the compositionapplied by the first application technique can range between anycombination of the recited values, inclusive of the recited values.

The first application technique in certain methods of the presentinvention may comprise any of a variety of application techniques suchas wiping, spraying, dipping, brushing, and flowing, among others. Incertain embodiments, the first application technique comprises wiping.As used herein, the term “wiping” refers to the act of moving an objecton the surface of a substrate with pressure and friction. In certainembodiments, the means for applying the composition comprising anadhesion promoting agent that is applied by the first applicationtechnique is an absorbent fibrous material. Non-limiting specificexamples of such materials include, for example, a paper towel, alint-free cloth, a sponge, a squeegee, or a UV wipe, among others.Commercially available products that are suitable for use as theabsorbent fibrous material in the methods and systems of the presentinvention include the Kimtech® Precision Wipes, commercially availablefrom Kimberly-Clark Corporation, Neenah, Wis.

In certain embodiments, the composition comprising an adhesion promotingagent that is applied by the first application technique is applied bywiping the surface with an absorbent fibrous material loaded with such acomposition. For example, an absorbent fibrous material may be loaded tosaturation with such a composition by immersing the material into thecomposition. Then, the absorbent fibrous material may, if desired, bepressed with weight to squeeze out excess and control loading of theabsorbent fibrous material.

In certain embodiments, the composition applied by the first applicationtechnique in the methods of the present invention is applied such that afilm thickness of less than 0.2 mils (5 micrometers), such as 0.001 to0.2 mils (0.025 to 5 micrometers), is formed on the substrate.

After applying the composition applied by the first applicationtechnique, the composition may be given a drying step in which solventis driven out of the composition by heating or an air drying periodbefore application of other compositions to the substrate. Suitabledrying conditions will depend on the particulars of the compositionapplied by the first application technique, and on the ambient humidityif the composition comprises an aqueous medium, but, in certainembodiments, a drying time of from 1 to 15 minutes, such as about 5minutes, at a temperature of 75° to 200° F. (21° to 93° C.) will besufficient.

In certain embodiments, the methods of the present invention alsocomprise the step of cleaning the substrate prior to applying anycomposition comprising an adhesion promoting agent to the substrate. Asused herein, the term “cleaning” refers to the removal of unwantedforeign matter from the surface, such as soil, dirt, cutting oils,waxes, finger oils, sanding dust, among other things. In certainembodiments, the substrate may be cleaned by, for example, mechanicallyseparating the unwanted matter from the substrate, dissolving theunwanted foreign matter, contacting the substrate with a detergent, or amixture of two or more of these methods.

As used herein, the term “detergent” refers to a substance that reducesthe surface tension of water; i.e., a surface-active agent, i.e., asurfactant, which concentrates at oil-water interfaces, exertsemulsifying action, and aids in removing contaminants from a surface.Examples of detergents that might be used in the practice of the presentinvention include, without limitation, the anionic, nonionic, andcationic surfactants described earlier, as well as soaps. In certainembodiments, the detergent comprises d-Limonene, an oil extracted fromcitrus rind.

In certain embodiments, the detergent is present in a cleaningcomposition. In these embodiments, the detergent may, for example,comprise 0.01 to 10.0 percent by weight or, in some embodiments 0.1 to0.5 percent by weight, or, in yet other embodiments 0.1 to 0.3 percentby weight of the cleaning composition based on the total weight thereof.In such embodiments, the amount of detergent present in the cleaningcomposition can range between any combination of the recited values,inclusive of the recited values.

In certain embodiments, the step of cleaning the substrate comprisescontacting the substrate with an object, such as a pad or sponge, havinga cleaning composition comprising a detergent in contact with orabsorbed therein. In certain embodiments, the step of cleaning thesubstrate comprises contacting the substrate with an abrasive materialhaving a cleaning composition comprising a detergent contained therein.Abrasive materials suitable for use in the methods and systems of thepresent invention are commercially available and include, for example,Scotch-Brite™ Scuff Sponges, commercially available from 3M Company, St.Paul, Minn., and Bear-Tex® Scuff Pads and Sponges, commerciallyavailable from Norton Abrasives.

In certain embodiments, the cleaning step comprises wiping the surfacewith an abrasive material loaded with a cleaning composition, such asthe compositions described above. For example, an abrasive material maybe loaded to saturation with such a composition by immersing theabrasive material into the composition. Then, the abrasive material may,if desired, be pressed with weight to squeeze out excess cleaningcomposition and control loading of the absorbent fibrous material.Indeed, one of the advantages of certain embodiments of the presentinvention is that, by loading an abrasive material with a cleaningcomposition, the cleaning and scuffing steps of a coating process can beperformed simultaneously.

In certain embodiments, the substrate is rinsed with water after thecleaning step and then dried. The drying step may, for example, simplybe sufficient to remove most of the rinse water from the substrate,though the water need not necessarily be removed in its entirety. Thesubstrate may be dried by any technique, such as wiping with a cloth,blow-drying, or simply air-drying, among other methods.

In certain embodiments, the step of cleaning the substrate comprisestreating the substrate, such as by corona treatment or similartreatments, to oxidize materials from the surface of the substrate priorto applying the compositions comprising an adhesion promoting agent.

As mentioned earlier, certain methods of the present invention alsocomprise the step of applying a composition comprising an adhesionpromoting agent to the substrate by a second application technique thatis different from the first application technique. In these methods, thecomposition applied by the second application technique is applied atleast partially over the composition applied by the first applicationtechnique.

In certain methods of the present invention, the adhesion promotingagent that is present in the composition applied by the secondapplication technique may include any of the adhesion promoting agentsdescribed earlier with respect to the composition applied by the firstapplication technique, such as halogenated polyolefins and halogenatedpolyolefins modified by grafting a compatibilizing material thereon,including mixtures thereof. The adhesion promoting agent present in thecomposition applied by the second application technique may be the sameas or different from the adhesion promoting agent present in thecomposition applied by the first application technique. In certainembodiments, the composition applied by the second application techniquemay also include any of the other materials identified above that may bepresent in the composition applied by the first application technique.

In certain embodiments, the composition comprising an adhesion promotingagent that is applied by the second application technique in certainmethods of the present invention is different than the compositioncomprising an adhesion promoting agent applied by the first applicationtechnique. For example, in certain embodiments, the adhesion promotingagent comprises 1 to 50 percent by weight or, in some embodiments, 1 to20 percent by weight, or, in yet other embodiments, 1 to 5 percent byweight of the composition applied by the second application technique incertain methods of the present invention based on the total weight ofthe composition. In such embodiments, the amount of adhesion promotingagent present in the composition applied by the second applicationtechnique can range between any combination of the recited values,inclusive of the recited values.

The second application technique may comprise any of a variety ofapplication techniques such as those that were identified earlier withrespect to the first application technique. In certain embodiments, thesecond application technique comprises spraying. Moreover, in certainembodiments, the composition comprising an adhesion promoting agent thatis applied by the second application technique in certain methods of thepresent invention is present in the form of a aerosol. In theseembodiments, the composition comprises a suspension of the adhesionpromoting agent in a gas, i.e., a propellant. In certain embodiments,the means for applying the composition comprising an adhesion promotingagent that is applied by the second application technique in certainmethods and systems of the present invention comprises a spray gun, suchas high volume—low pressure (HVLP), airless, air assisted airless, andelectrostatic enhanced spray guns, among others.

In other embodiments, the means for applying the composition comprisingan adhesion promoting agent that is applied by the second applicationtechnique in certain methods and systems of the present inventioncomprises a pressurized container containing the composition in aerosolform as described above. In these embodiments, the propellant maycomprise 10 to 50 percent by weight or, in some embodiments, 20 to 40percent by weight, or, in yet other embodiments, 25 to 35 percent byweight of the composition applied by the second application techniquebased on the total weight of the composition. In such embodiments, theamount of propellant present in the composition applied by the secondapplication technique can range between any combination of the recitedvalues, inclusive of the recited values.

In certain embodiments, the composition applied by the secondapplication technique is applied such that a film thickness of less than0.2 mils (5 micrometers), such as 0.001 to 0.2 mils (0.025 to 5micrometers), is formed on the substrate. After applying the compositionapplied by the second application technique, the composition may begiven a drying step, such as that described earlier with respect to thecomposition applied by the first application technique.

The methods of the present invention also comprise the step of applyinga protective and decorative coating system to at least a portion of thesubstrate, wherein the coating system is applied at least partially overat least one of the composition(s) described earlier.

Protective and decorative coating systems that may be used in themethods of the present invention include, for example, those protectiveand decorative coating systems that are conventionally used inautomotive refinish coating applications and automotive OEMapplications, among others. Examples of suitable protective anddecorative coating systems that may be applied in accordance with themethods of the present invention include single layer coating systems,such as pigmented direct gloss coating systems, and multi-layeredsystems, such as systems that include a pigmented basecoat layer and aclear top coating layer. Such coating systems may also include a primerlayer, as will be understood by those skilled in the art.

In certain embodiments, one or more layers of the protective anddecorative coating system may be deposited from a coating compositionthat includes a thermosetting polymeric composition. As used herein, theterm “thermosetting” refers to polymeric compositions that “set”irreversibly upon curing or crosslinking, wherein the polymer chains ofthe polymeric components are joined together by covalent bonds. Thisproperty is usually associated with a cross-linking reaction of thecomposition constituents often induced, for example, by heat orradiation. See Hawley, Gessner G., The Condensed Chemical Dictionary,Ninth Edition., page 856; Surface Coatings, vol. 2, Oil and ColourChemists' Association, Australia, TAFE Educational Books (1974). Curingor crosslinking reactions also may be carried out under ambientconditions. Once cured or crosslinked, a thermosetting resin will notmelt upon the application of heat and is insoluble in solvents. In otherembodiments, one or more layers of the protective and decorative coatingsystem may be deposited from a coating composition that includes athermoplastic polymeric composition. As used herein, the term“thermoplastic” refers to polymeric compositions that comprise polymericcomponents that are not joined by covalent bonds and thereby can undergoliquid flow upon heating and are soluble in solvents. See Saunders, K.J., Organic Polymer Chemistry, pp. 41-42, Chapman and Hall, London(1973).

In certain embodiments, one or more layers of the protective anddecorative coating system may be deposited from a liquid compositionthat includes a polymeric composition and a diluent, that is, waterborneor solventborne systems. Suitable diluents include organic solvents,water, and water/organic solvent mixtures. Organic solvents in whichsuch polymeric compositions may be dispersed include, for example,alcohols, ketones, aromatic hydrocarbons, glycol ethers, esters, andmixtures thereof. The diluent is sometimes present in amounts rangingfrom 5 to 80 weight percent based on the total weight of thecompositions, such as 30 to 50 weight percent.

In certain embodiments, one or more layers of the protective anddecorative coating system may be deposited from a coating compositionthat includes a polymeric composition that includes, without limitation,hydroxyl or carboxylic acid-containing acrylic copolymers, hydroxyl orcarboxylic acid-containing polyester polymers and oligomers, isocyanateor hydroxyl-containing polyurethane polymers, and/or amine orisocyanate-containing polyureas.

Acrylic polymers, if used, are typically copolymers of acrylic acid ormethacrylic acid or hydroxyalkyl esters of acrylic or methacrylic acidsuch as hydroxyethyl methacrylate or hydroxypropyl acrylate with one ormore other polymerizable ethylenically unsaturated monomers such asalkyl esters of acrylic acid including methyl methacrylate and 2-ethylhexyl acrylate, and vinyl aromatic compounds such as styrene,alpha-methyl styrene and vinyl toluene. The ratio of reactants andreaction conditions are selected to result in an acrylic polymer withpendant hydroxyl or carboxylic acid functionality.

Besides acrylic polymers, one or more layers of the protective anddecorative coating system may be deposited from a coating compositionthat includes a polymeric composition that includes a polyester polymeror oligomer. Such polymers may be prepared in a known manner bycondensation of polyhydric alcohols and polycarboxylic acids. Suitablepolyhydric alcohols include, for example, ethylene glycol, neopentylglycol, trimethylol propane and pentaerythritol.

Suitable polycarboxylic acids include, for example, adipic acid,1,4-cyclohexyl dicarboxylic acid and hexahydrophthalic acid. Besides thepolycarboxylic acids mentioned above, functional equivalents of theacids such as anhydrides where they exist or lower alkyl esters of theacids such as the methyl esters may be used. Also, small amounts ofmonocarboxylic acids such as stearic acid may be used.

Hydroxyl-containing polyester oligomers can be prepared by reacting ananhydride of a dicarboxylic acid such as hexahydrophthalic anhydridewith a diol such as neopentyl glycol in a 1:2 molar ratio.

Where it is desired to enhance air-drying, suitable drying oil fattyacids may be used and include, for example, those derived from linseedoil, soya bean oil, tall oil, dehydrated castor oil or tung oil, amongothers.

The polyesters may, for example, contain free terminal hydroxyl and/orcarboxyl groups that are available for further crosslinking reactions.

Polyurethane polymers containing terminal isocyanate or hydroxyl groupsmay also be present in the coating compositions from which one or morelayers of the protective and decorative coating systems are deposited.Polyurethane polyols or NCO-terminated polyurethanes that can be usedinclude, for example, those prepared by reacting polyols includingpolymeric polyols with polyisocyanates. The polyurea-containing terminalisocyanate or primary or secondary amine groups which can be usedinclude, for example, those prepared by reacting polyamines includingpolymeric polyamines with polyisocyanates. The hydroxyl/isocyanate oramine/isocyanate equivalent ratio is adjusted and reaction conditionsselected to obtain the desired terminal group. Examples of suitablepolyisocyanates include those described in U.S. Pat. No. 4,046,729 atcolumn 5, line 26 to column 6, line 28, incorporated herein byreference. Examples of suitable polyols include those described in U.S.Pat. No. 4,046,729 at column 7, line 52 to column 10, line 35,incorporated herein by reference. Examples of suitable polyaminesinclude those described in U.S. Pat. No. 4,046,729 at column 6, line 61to column 7, line 32 and in U.S. Pat. No. 3,799,854 at column 3, lines13 to 50, both incorporated herein by reference.

In certain embodiments, one or more layers of the protective anddecorative coating system may be deposited from a curable coatingcomposition that includes a curing agent, such as aminoplast resins andphenoplast resins and mixtures thereof, as curing agents for OH andCOOH, and amide and carbamate functional group containing materials.Examples of aminoplast and phenoplast resins suitable as curing agentsin such curable compositions include those described in U.S. Pat. No.3,919,351 at col. 5, line 22 to col. 6, line 25, incorporated herein byreference.

Polyisocyanates and blocked polyisocyanates as curing agents for OH andprimary and/or secondary amino group containing materials are well knownin the art. Examples of suitable polyisocyanates and blocked isocyanatesinclude those described in U.S. Pat. No. 4,546,045 at col. 5, lines 16to 38; and in U.S. Pat. No. 5,468,802 at col. 3, lines 48 to 60, bothincorporated herein by reference.

Anhydrides as curing agents for OH and primary and/or secondary aminogroup containing materials are well known in the art. Examples ofsuitable anhydrides include those described in U.S. Pat. No. 4,798,746at col. 10, lines 16 to 50 and in U.S. Pat. No. 4,732,790 at col. 3,lines 41 to 57, both incorporated herein by reference.

Polyepoxides as curing agents for COOH functional group containingmaterials are well known in the art. Examples of suitable polyepoxidesinclude those described in U.S. Pat. No. 4,681,811 at col. 5, lines 33to 58, incorporated herein by reference.

Polyacids as curing agents for epoxy functional group containingmaterials are well known in the art. Examples of suitable polyacidsinclude those described in U.S. Pat. No. 4,681,811 at col. 6, line 45 tocol. 9, line 54, incorporated herein by reference.

Polyols, that is, a material having an average of two or more hydroxylgroups per molecule, can be used as curing agents for NCO functionalgroup containing materials and anhydrides and esters and are well knownin the art. Examples of suitable polyols include those described in U.S.Pat. No. 4,046,729 at col. 7, line 52 to col. 8, line 9; col. 8, line 29to col. 9, line 66 and in U.S. Pat. No. 3,919,315 at col. 2, line 64 tocol. 3, line 33, both incorporated herein by reference.

Polyamines can also be used as curing agents for NCO functional groupcontaining materials and for carbonates and unhindered esters and arewell known in the art. Examples of suitable polyamines include thosedescribed in U.S. Pat. No. 4,046,729 at col. 6, line 61 to col. 7, line26, incorporated herein by reference.

In certain embodiments, one or more layers of the protective anddecorative coating system may be deposited from a coating compositionthat includes, in addition to the components described above, a varietyof other adjuvant materials. If desired, other polymeric compositionscan be utilized in conjunction with the polymeric compositions describedabove so long as the resultant coating composition is not detrimentallyaffected in terms of application, physical performance and appearanceproperties.

In certain embodiments, one or more layers of the protective anddecorative coating system may be deposited from a coating compositionthat includes a catalyst to accelerate the cure reaction. Examples ofsuitable catalysts include organotin compounds such as dibutyl tindilaurate, dibutyl tin oxide and dibutyl tin diacetate. Catalystssuitable for promoting the cure reaction between an aminoplast curingagent and the reactive hydroxyl and/or carbamate functional groups ofthe thermosettable dispersion include acidic materials, for example,acid phosphates such as phenyl acid phosphate, and substituted orunsubstituted sulfonic acids such as dodecylbenzene sulfonic acid orparatoluene sulfonic acid.

In certain embodiments, one or more layers of the protective anddecorative coating system may be deposited from a coating compositionthat includes one or more other additive ingredients, including thosewhich are well known in the art of formulating surface coatings, such asdyes, pigments, surfactants, flow control agents, thixotropic agents,fillers, anti-gassing agents, organic co-solvents, catalysts, and othercustomary auxiliaries. Examples of these materials and suitable amountsare described in U.S. Pat. Nos. 4,220,679, 4,403,003, 4,147,769 and5,071,904, which are incorporated herein by reference.

In certain embodiments, a protective and decorative coating system isapplied to the substrate, wherein the coating system comprises a coatinglayer deposited from a coating composition that comprises an adhesionpromoting agent. Such a composition includes a resin that is compatiblewith the adhesion promoting agent and may be applied by any suitableapplication technique. In these embodiments, the composition maycomprise a halogenated polyolefin that is modified by grafting acompatibilizing material onto the polyolefin as described above. Forexample, if a primer layer is present in the protective and decorativecoating system, then the composition from which such a layer isdeposited may include such an adhesion promoting agent. On the otherhand, if such a layer is not present, the adhesion promoting agent maybe present in the basecoat of a multi-layered coating system or it maybe present in the composition from which the single coat of a singlelayer coating system is deposited. In certain embodiments, the adhesionpromoting agent may be present in more than one layer of the protectiveand decorative coating system.

Therefore, certain methods of the present invention comprise the stepsof (a) applying a composition comprising an adhesion promoting agent toat least a portion of a plastic substrate by a first applicationtechnique; and (b) applying a protective and decorative coating systemover at least a portion of the composition applied in step (a). In thesemethods of the present invention, the protective and decorative coatingsystem comprises a coating layer deposited from a coating compositionthat comprises an (i) adhesion promoting agent comprising a halogenatedpolyolefin that, in certain embodiments, may be modified by grafting acompatibilizing material onto the polyolefin, and (ii) a resin that iscompatible with the adhesion promoting agent. Such resins may includeany of the thermosetting or thermoplastic polymeric compositionsdescribed earlier. Moreover, such a coating layer may be deposited by anapplication technique that is the same as or different from the firstapplication technique.

In certain embodiments, a coating layer of the protective and decorativecoating system is deposited from a composition that comprises 0.1 to20.0 percent by weight, or, in some cases, 0.1 to 10.0 percent byweight, or, in other embodiments, 1.0 to 5.0 percent by weight of theadhesion promoting agent based on the total weight of the composition.The amount of the adhesion promoting agent present in such coatingcompositions may range between any combination of these values,inclusive of the recited values.

The coating compositions from which one or more layers of the protectiveand decorative coating system are deposited may be applied by anyconventional coating technique, such as brushing, spraying, dipping, orflowing, among others. In certain embodiments, such compositions areapplied by spraying. Moreover, in certain embodiments, the means forapplying such compositions comprises a spray gun, such as those thatwere described earlier, or an aerosol can.

As will be appreciated by the foregoing description, the presentinvention is also directed to methods for coating articles having aplastic substrate, which comprise the steps of (a) applying a firstcomposition comprising an adhesion promoting agent to at least a portionof the substrate; (b) applying a second composition comprising anadhesion promoting agent over at least a portion of the compositionapplied in step (a); and (c) applying a protective and decorativecoating system over at least a portion of the composition applied insteps (a) and (b). In these embodiments, the first and secondcompositions are different and at least one of the compositionscomprising an adhesion promoting agent may be applied to the substrateby wiping. Moreover, in certain embodiments, one of the compositionscomprising an adhesion promoting agent may be applied by wiping and theother may be applied by spraying.

As will also be appreciated by the foregoing description, the presentinvention is also directed to systems for coating articles having aplastic substrate. In certain embodiments, the systems of the presentinvention comprise: (a) means for applying a composition comprising anadhesion promoting agent to at least a portion of the substrate by afirst application technique; (b) means for applying a compositioncomprising an adhesion promoting agent to the substrate by a secondapplication technique that is different from the first applicationtechnique; and (c) means for applying a protective and decorativecoating system to at least a portion of the substrate.

In certain embodiments, certain elements of the systems of the presentinvention may be provided in the form of a kit. For example, the kit maycomprise a cleaning tool, such as an abrasive material having adetergent contained therein as described earlier, and a means forapplying a composition comprising an adhesion promoting agent to atleast a portion of the substrate by a first application technique, suchas the absorbent fibrous material comprising such a composition, asdescribed earlier. In addition, the kit may also include a means forapplying a composition comprising an adhesion promoting agent to atleast a portion of the substrate by a second application technique, suchas the spray gun or pressurized container containing the composition inaerosol form as described earlier.

The present invention provides methods and systems for coating articlescomprising a plastic substrate. Such methods can be less complex,wasteful, labor intensive, and/or time-consuming as compared to priorart methods of coating articles having a plastic substrate. Moreover,because an adhesion promoting agent is applied in more than one step ofthe coating methods and systems of the present invention, these methodsand systems can, in certain cases, provide more consistent adhesionresults as compared to prior art coating methods, particularly in a bodyshop setting.

Illustrating the invention are the following examples, which, however,are not to be considered as limiting the invention to their details.Unless otherwise indicated, all parts and percentages in the followingexamples, as well as throughout the specification, are by weight.

EXAMPLES

The following Examples A, B, C, D, E and F describe the preparation ofcompositions comprising adhesion promoting agents comprising a modifiedchlorinated polyolefin. Example G describes the preparation of a scuffpad having a cleaning composition comprising a detergent absorbedtherein. Examples 1 to 7 describe the application of compositionscomprising an adhesion promoting agent to various articles comprising aplastic substrate, in accordance with embodiments of the methods andsystems of the present invention.

Example A

A composition comprising an adhesion promoting agent comprising achlorinated polyolefin having an acrylic monomer grafted thereon wasprepared by adding Charge I (1163.2 parts by weight toluene and 320.0parts by weight of CP-343-1, a chlorinated polyolefin commerciallyavailable from Eastman Chemical Products, Inc., of Rochester, N.Y.),under agitation and a nitrogen blanket to a 5 liter round bottom glassreaction vessel equipped with a stirrer, a condenser, two feed ports andmeans for maintaining a nitrogen blanket. The mixture was brought toreflux and then the nitrogen blanket was discontinued. Charge 2 (360.0parts by weight of butyl methacrylate and 120.0 parts by weight ofhydroxypropyl methacrylate) and Charge 3 (1120.0 parts by weight tolueneand 16.0 parts by weight Luperox 26, t-butyl peroxy-2-ethylhexanoatecommercially available from Atofina Canada Inc., Ontario, Canada) wereadded uniformly and simultaneously to the vessel over a two hour periodwhile maintaining reflux conditions. Upon completion of Charges II andIII, Charge IV (200.0 parts by weight toluene and 4.0 parts by weightLuperox 26) was added over a 30 minute period followed by a 30 minutehold period maintaining reflux conditions. The resulting polymer had asolids content of 22.6%, an —OH number of 14.3, and a weight averagemolecular weight of 28,109 as determined by gel permeationchromatography using a polystyrene standard.

Example B

A composition comprising an adhesion promoting agent comprising achlorinated polyolefin having an acrylic monomer grafted thereon wasprepared by adding Charge I (1400.0 parts by weight xylene, 600.0 partsby weight of CP-343-1, and 100.0 parts by weight cyclohexene oxide),under agitation and a nitrogen blanket to a 5 liter round bottom glassreaction vessel equipped with a stirrer, a condenser, two feed ports andmeans for maintaining a nitrogen blanket. The mixture was heated to 80°C. under a nitrogen blanket at 0.2 cubic feet per minute and held for1.5 hours. Charge II (10.20 parts by weight of 2,2′-Bipyridyl, 3.05parts by weight of Copper, and 60.0 parts by weight of butyl acetate)was added and held for 15 minutes. Charge III (225.0 parts by weight ofhydroxyl propyl methacrylate and 675.0 parts by weight of butylmethacrylate) was then added over a two hour period. The mixture washeld until a total solids of 48-52% was achieved. Charge IV (950.0 partsby weight of butyl acetate, 950.0 parts by weight of xylene, and 25.5parts by weight of acetic acid) was then added. Charge V (1.5% based ontotal reaction solids of Amberlite® IRC 748: ion-exchange resinavailable Acros Organics N.V., Fair Lawn, N.J.) was then added and thereaction was held for 1.5 hours at 85° C. The reaction product wasfiltered through a 5 micron bag and then a 1 micron bag. The resultingproduct had a solids content of 22%, and a weight average molecularweight of 64,797 as determined by gel permeation chromatography using apolystyrene standard.

Example C

A composition comprising an adhesion promoting agent comprising achlorinated polyolefin having an acrylic monomer grafted thereon wasprepared in the same manner as described in Example A, with oneexception. To Charge I was added 1 weight percent based on the totalsolids weight of Cardura E, an aliphatic mono glycidyl functionalmaterial, commercially available from Resolution Performance ProductsLLC, Houston, Tex.

Example D

A composition comprising an adhesion promoting agent comprising achlorinated polyolefin having an acrylic monomer grafted thereon wasprepared in the same manner as described in Example A, with oneexception. To Charge I was added 1 weight percent of glycidylmethacrylate based on the total solids weight of Charge 1.

Example E

A composition comprising an adhesion promoting agent comprising amodified chlorinated polyolefin dispersed in an aqueous medium wasprepared as follows. In a suitably equipped container, 3.3 parts byweight of Aerosol OT-75 (an anionic surfactant commercially availablefrom Cytec Industries, Inc., West Paterson, N.J.) and 790.2 parts byweight of distilled water were mixed for 10 minutes. To this stirredsolution, 206.5 parts by weight of the adhesion promoting agent preparedin Example B was added over 15 minutes, and then the mixture was stirredfor 30 minutes. The resulting composition had a solids content of 4.02%and a pH of 4.94.

Example F

A composition comprising an adhesion promoting agent comprising amodified chlorinated polyolefin dispersed in an aqueous medium wasprepared as follows. In a suitably equipped container, 3.3 parts byweight of Aerosol OT-75 and 790.2 parts by weight of distilled waterwere mixed for 10 minutes. To this stirred solution, 206.5 parts byweight of the adhesion promoting agent prepared in Example A was addedover 15 minutes, and then the mixture was stirred for 30 minutes. 3.75parts by weight of 25 weight percent dimethylethanolamine in water wasthen added to the mixture over 1 minute and stirred for 15 minutes. Theresulting composition had a solids content of 4.7% and a pH of 8.6.

Example G

A cleaning composition was prepared by mixing 754.25 parts by weight ofdeionized water with 81.3 parts by weight of d-Limonene. A Scotch-Brite®Scuff Sponge (gray or gold), commercially available from 3M Company, St.Paul, Minn., was loaded to saturation with the cleaning composition byimmersing the Scuff Sponge into a container of the cleaning composition.Any excess cleaning composition was allowed to drip off of the ScuffSponge.

Example 1

Automobile bumpers supplied from various automobile manufacturers andcomprising a thermoplastic polyolefin substrate were subjected tocoating processes wherein an adhesion promoting agent was applied to thesubstrate. Examples 1A through 1E in Table 1 were prepared as follows.The area of the substrate to be painted was wiped with a saturated ScuffSponge prepared as described in Example G. After drying, a compositioncomprising an adhesion promoting agent (specified as “Ad Pro Wipe Type”in Table 1) was wiped onto the area of the substrate to be painted. Thewipe was prepared by pouring the composition identified in Table 1 ontoa Kimtech® Precision Wipe, commercially available from Kimberly-ClarkCorporation, and allowing the excess to drip off of the wipe. Afterdrying, a second composition comprising an adhesion promoting agent(specified as “Ad Pro Spray Type” in Table 1) was sprayed onto the areaof the substrate to be painted using a HVLP (high volume low pressure)hand spray gun. After drying, the substrate was painted with BC4329basecoat and D893 low VOC clearcoat, both of which are commerciallyavailable from PPG Industries, Inc., in accordance with the instructionsprovided on the product data sheet supplied by the manufacturer.

Comparative Examples 1F through 1J in Table 1 were prepared as follows.The area to be painted was washed with soap and water and cleaned withDX 330 Acrylic Cleaner commercially available from PPG Industries, Inc.After drying, the area of the substrate to be painted was scuffed with agold Scotch-Brite® Scuff Sponge. The area was then cleaned again with DX330 and any excess was removed with a clean damp cloth. The area of thesubstrate to be painted was then wiped with DX 103, a wipe containing anantistatic agent, which is commercially available from PPG Industries,Inc. After drying, a composition comprising an adhesion promoting agentwas sprayed onto the area of the surface to be painted using a HVLP handspray gun. After drying, the substrate was painted with BC4329 basecoatand D893 low VOC clearcoat, as described above. The results are reportedin Table 1.

TABLE 1 Ad Pro Wipe Ad Pro 24 hour Example Substrate Type Type SprayType Adhesion⁴ 1A Nissan  A¹  B² 100% 1B Toyota A B 100% 1C ChryslerSmooth A B 100% 1D Chrysler Textured A B 100% 1E Subaru A B 100%Comparative 1F Nissan None  C³ 100% Comparative 1G Toyota None C 95%Comparative 1H Chrysler Smooth None C 100% Comparative 1I ChryslerTextured None C 55% Comparative 1J Subaru None C 45% ¹Ad Pro Wipe Type Awas prepared by reducing the composition prepared in Example A to 2%solids using P273-1050, a solvent blend that includes an anti-staticagent, commercially available from PPG Industries, Inc ²Ad Pro SprayType B was prepared by reducing the composition prepared in Example A to5% solids using xylene. ³Ad Pro Spray Type C was DPX 801, an adhesionpromoting composition comprising a chlorinated polyolefin, commerciallyavailable from PPG Industries, Inc. ⁴24 hour coating adhesion wasevaluated using a Crosshatch adhesion test. Using a multi-blade cutter(Paul N. Gardner Company, Inc.), coated panels were scribed twice (at90°), making sure the blades cut through all coating layers into thesubstrate. Coating adhesion was measured using Nichiban L-24 tape (fourpulls at 90°). Failure mode was adhesive between the substrate andadhesion promoter, unless otherwise noted in the results. Adhesionmeasurements were taken after one day of ambient cure of the coatingafter application. Results are reported in %, wherein 100% represents nocoating adhesion failure.

Example 2

Thermoplastic polyolefin (“TPO”) and polypropylene (“PP”) substrateswere subjected coating processes wherein an adhesion promoting agent wasapplied to the substrate. Step 1 of the process comprised wiping thesurface to be painted with a Scuff Sponge saturated with a cleaningcomposition prepared as described in Example G. Step 2 of the processcomprised wiping the surface to be painted with a composition preparedby reducing the composition prepared in Example A to 1% solids usingP273-1050. The wipe was prepared by pouring that composition onto aKimtech® Precision Wipe and allowing the excess to drip off of the wipe.Step 3 of the process comprised spraying the surface to be painted witha composition prepared by reducing the composition prepared in Example Ato 5% solids using xylene. The composition was sprayed onto the area ofthe substrate to be painted using a HVLP hand spray gun. In eachExample, at least two of Steps 1 to 3 were performed, as described inTable 2. In the Comparative Examples identified in Table 2, either Step2 or Step 3 was omitted. After drying, the substrate was painted withBC4320 basecoat and D893 low VOC clearcoat, in accordance with themanufacturer's instructions. Results are reported in Table 2.

TABLE 2 Adhesion Substrate Perform Perform Perform Adhesion Adhesion 10day Example Type Step 1? Step 2? Step 3? 24 hr⁵ 7 day⁶ humidity⁷ 2A PPYes Yes Yes 100% 100% 100% (35% bc/coh)⁸ Comparative PP Yes Yes No  84%100% 100% (25% 2B bc/ad pro) Comparative PP Yes No Yes 100%  90% 100%(90% 2C bc/coh) 2D PP No Yes Yes 100% 100% 100% (75% bc/coh) 2E TPO YesYes Yes 100% 100% 100% (100% bc/coh) Comparative TPO Yes Yes No 100%100% 100% (75% 2F bc/coh) Comparative TPO Yes No Yes 100% 100% 100%(100% 2G bc/coh) 2H TPO No Yes Yes 100% 100% 100% (86% bc/coh) ⁵24 hourcoating adhesion was measured as described above in Table 1. ⁶7 dayscoating adhesion was evaluated in the same manner as the 24 hour coatingadhesion, except that adhesion measurements were taken after seven daysof ambient cure of the coating after application. ⁷10 day humiditycoating adhesion was evaluated in the same manner as the 24 hour coatingadhesion, except that adhesion measurements were taken after ten days ofcure of the coating at 100° F. and 100% relative humidity. ⁸“bc/coh”identifies cohesive splitting of the basecoat (failure of the basecoat).Results are reported in %, wherein 100% represents no splitting of thebasecoat.

Example 3

Thermoplastic polyolefin (“TPO”) and polypropylene (“PP”) substrateswere subjected coating processes wherein an adhesion promoting agent wasapplied to the substrate. First, the surface to be painted was wipedwith a Scuff Sponge saturated with a cleaning composition prepared asdescribed in Example G. After rinsing with water and drying, the surfaceto be painted was wiped with a composition comprising an adhesionpromoting agent. The compositions and preparation of the wipes isdescribed in Table 3 and identified as “Ad Pro Wipe”. As is apparent, incertain Comparative Examples, this wiping step was omitted. Afterallowing to dry, the surface to be painted was sprayed with acomposition prepared by reducing the composition prepared in Example Ato 5 percent solids using xylene. That composition was sprayed onto thearea of the substrate to be painted using a HVLP hand spray gun. InComparative Examples 3C, 3D, 3G, 3H, 3K, 3L, 3O, 3P, 3S, and 3T, thisspraying step was omitted. After drying, the substrate was painted withBC3964 basecoat and D893 low VOC clearcoat, in accordance with themanufacturer's instructions. Results are reported in Table 3.

TABLE 3 Ad Pro Adhesion Adhesion Adhesion 10 Example Substrate Wipe Type24 hr⁹ 7 day¹⁰ day humidity¹¹ 3A TPO D¹² 100% 100% 100% 3B PP D 100%100% 100% Comparative 3C TPO D 100% 100% 100% Comparative 3D PP D 100%100% 100% 3E TPO E¹³ 100% 100% 100% 3F PP E 100% 100% 100% Comparative3G TPO E 100% 100% 100% Comparative 3H PP E 100% 100% 100% 3I TPO F¹⁴100% 100% 100% 3J PP F 15% 20% 80% Comparative 3K TPO F 76% 92% 80%Comparative 3L PP F 0% 10% 0% 3M TPO G¹⁵ 65% 75% 90% 3N PP G 0% 60% 0%Comparative 3O TPO G 98% 100% 99% Comparative 3P PP G 65% 60% 20%Comparative 3Q TPO None 100% 100% 100% Comparative 3R PP None 15% 60%25% Comparative 3S TPO None 0% 0% 0% Comparative 3T PP None 0% 0% 0% ⁹24hour coating adhesion was measured as described above in Table 1. ¹⁰7days coating adhesion was evaluated as described above in Table 2. ¹¹10day humidity coating adhesion was evaluated as described above in Table2. ¹²Ad Pro Wipe Type D was prepared by reducing the compositionprepared in Example B to 5% solids using xylene. The wipe was preparedby pouring that composition onto a Kimtech ® Precision Wipe and allowingthe excess to drip off of the wipe. ¹³Ad Pro Wipe Type E was prepared byreducing the composition prepared in Example A to 5% solids usingxylene. The wipe was prepared by pouring that composition onto aKimtech ® Precision Wipe and allowing the excess to drip off of thewipe. ¹⁴Ad Pro Wipe Type F was prepared by pouring the compositionprepared in Example E onto a Kimtech ® Precision Wipe and allowing theexcess to drip off of the wipe. ¹⁵Ad Pro Wipe Type G was prepared bypouring the composition prepared in Example F onto a Kimtech ® PrecisionWipe and allowing the excess to drip off of the wipe.

Example 4

Thermoplastic polyolefin (“TPO”) and polypropylene (“PP”) substrateswere subjected to coating processes wherein an adhesion promoting agentwas applied to the substrate. Step 1 of the process comprised wiping thesurface to be painted with a Scuff Sponge saturated with a cleaningcomposition prepared as described in Example G. Step 2 of the processcomprised wiping the surface to be painted with a composition preparedby reducing the composition prepared in Example A to 1% solids usingP273-1050. The wipe was prepared by pouring that composition onto aKimtech® Precision Wipe and allowing the excess to drip off of the wipe.After allowing to dry, the surface to be painted was sprayed with acomposition comprising an adhesion promoting agent. The compositions andtheir applications are described in Table 4 and identified as “Ad ProSpray”. In the Comparative Examples identified in Table 4, Step 2 wasomitted. After drying, the substrate was painted with BC4329 basecoatand D893 low VOC clearcoat, in accordance with the manufacturer'sinstructions. Results are reported in Table 4.

TABLE 4 Adhesion Example Substrate Ad Pro Spray 24 hr¹⁶ Comparative 4ATPO  B¹⁷ 100% Comparative 4B PP B 100% 4C TPO B 100% 4D PP B 100%Comparative 4E TPO  H¹⁸ 100% Comparative 4F PP H 35% 4G TPO H 100% 4H PPH 100% Comparative 4I TPO  I¹⁹ 100% Comparative 4J PP I 90% 4K TPO I100% 4L PP I 100% ¹⁶24 hour coating adhesion was measured as describedabove in Table 1. ¹⁷Ad Pro Spray type B was prepared and applied asdescribed in Table 1 above. ¹⁸Ad Pro Spray type H was an aerosolcomposition comprising 86.3 parts by weight of the composition preparedin Example A, 345.1 parts by weight xylene, and 184.9 parts by weight ofAeron ® NP-70 Gas mixture commercially available from DiversifiedChemicals & Propellants Co., Hinsdale, Illinois. The aerosol compositionwas prepared by placing the Example A composition and xylene into aspray can and then vacuuming the can. The gas mixture was injected intothe can and the can was pressurized until the can contained all of thegas mixture. The aerosol composition was then sprayed onto the area ofthe substrate to be painted. ¹⁹Ad Pro Spray type I was an aerosolcomposition comprising 44.4 parts by weight of the composition preparedin Example A, 158.1 parts by weight xylene, and 86.8 parts by weight ofa propane, n-butane, i-butane gas mixture from Peter Kwasny GmbH,Gundelsheim, Germany. The aerosol composition was prepared by placingthe Example A composition and xylene into a spray can and then vacuumingthe can. The gas mixture was injected into the can and the can waspressurized until the can contained all of the gas mixture. The aerosolcomposition was then sprayed onto the area of the substrate to bepainted.

Example 5

Thermoplastic polyolefin (“TPO”) and polypropylene (“PP”) substrateswere subjected coating processes wherein an adhesion promoting agent wasapplied to the substrate. Step 1 of the process comprised wiping thesurface to be painted with a Scuff Sponge saturated with a cleaningcomposition prepared as described in Example G. After rinsing with waterand drying, step 2 of the process comprised wiping the surface to bepainted with a composition prepared by reducing the composition preparedin Example A to 1% solids using P273-1050. The wipe was prepared bypouring that composition onto a Kimtech® Precision Wipe and allowing theexcess to drip off of the wipe. Step 3 of the process comprised sprayingthe surface to be painted with a composition prepared by reducing thecomposition prepared in Example A to 5% solids using xylene. Thecomposition was sprayed onto the area of the substrate to be paintedusing a HVLP hand spray gun. After allowing to dry, step 4 of theprocess comprised spraying the surface to be painted with a primercoating composition using a HVLP hand spray gun. These primer coatingcompositions are described in Table 5 and identified as “Primer”. Insome cases, Step 3 was omitted as indicated in Table 5. After step 4,the substrate was painted with BC4295 basecoat and D893 low VOCclearcoat, in accordance with the manufacturer's instructions. Resultsare reported in Table 5.

TABLE 5 Step 3 Adhesion Adhesion Adhesion Example Substrate Performed?Primer 24 hr²⁰ 7 day²¹ 10 day humidity²² 5A TPO Yes J²³ 100% 100% 100%(90% bc/coh)²⁷ 5B PP Yes J 100% 100% 100% (20% bc/coh) 5C TPO No K²⁴100% 100% 100% (80% bc/coh) 5D PP No K 100% 100% 100% (90% bc/coh) 5ETPO No L²⁵ 100% 100% 100% (55% bc/coh) 5F PP No L 100% 100% 100% (95%bc/coh) 5G TPO No M²⁶ 100% 100% 100% (45% bc/coh) 5H PP No M 100% 100%100% (45% bc/coh) % ²⁰24 hour coating adhesion was measured as describedabove in Table 1. ²¹7 days coating adhesion was evaluated as describedabove in Table 2. ²²10 day humidity coating adhesion was evaluated asdescribed above in Table 2. ²³Primer J comprised a mixture of 185 partsby weight of P565-510, a resin commercially available from PPGIndustries, Inc., 19.5 parts by weight of P210-796, a hardenercommercially available from PPG Industries, Inc., and 20.6 parts byweight of P850-1693, a reducer commercially available from PPGIndustries, Inc. ²⁴Primer K comprised a mixture of 185 parts by weightof P565-510, 19.5 parts by weight of P210-796, 20.6 parts by weight ofP850-1693, and 3.7 parts by weight of the composition prepared inExample A. ²⁵Primer L comprised a mixture of 185 parts by weight ofP565-510, 19.5 parts by weight of P210-796, 20.6 parts by weight ofP850-1693, and 6.2 parts by weight of the composition prepared inExample A. ²⁶Primer M comprised a mixture of 185 parts by weight ofP565-510, 19.5 parts by weight of P210-796, 20.6 parts by weight ofP850-1693, and 12.4 parts by weight of the composition prepared inExample A. ²⁷“bc/coh” refers to cohesive splitting of the basecoat asdescribed in Table 2 above.

Example 6

Thermoplastic polyolefin (“TPO”) and polypropylene (“PP”) substrateswere subjected coating processes wherein an adhesion promoting agent wasapplied to the substrate. Step 1 of the process comprised wiping thesurface to be painted with a Scuff Sponge saturated with a cleaningcomposition prepared as described in Example G. After rinsing with waterand drying, step 2 of the process comprised wiping the surface with AdPro Wipe Type D identified in Table 3 above. The wipes were prepared bypouring that composition onto a Kimtech® Precision Wipe and allowing theexcess to drip off of the wipe. As is apparent in Table 6, in certainComparative Examples, this wiping step was omitted. After allowing todry, step 3 of the process comprised spraying the surface to be paintedwith a composition comprising an adhesion promoting agent. The variouscompositions used are described in Table 6 and identified as “Ad ProSpray”. The composition was sprayed onto the area of the substrate to bepainted using a HVLP hand spray gun. As is apparent, in certainComparative Examples, this spraying step was omitted. After drying, thesubstrate was painted with BC4320 basecoat and DCU-2042 clearcoat, inaccordance with the manufacturer's instructions. Results are reported inTable 6.

TABLE 6 Ad Pro Ad Pro Adhesion Adhesion Adhesion Example Substrate Wipe?Spray 24 hr²⁸ 7 day²⁹ 10 day humidity³⁰ Comparative 6A TPO Yes None 100%100% 100% Comparative 6B PP Yes None 100% 100% 100% Comparative 6C TPONo O³¹ 100% 100% 100% Comparative 6D PP No O 100% 100% 100% Comparative6E TPO No B³² 100% 100% 100% Comparative 6F PP No B 100% 100% 100%Comparative 6G TPO No B 100% 100% 100% Comparative 6H PP No B 100% 100%100% (90% bc/coh) Comparative 6I TPO No C³³ 100% 100% 100% Comparative6J PP No C 100% 100% 100% 6K TPO Yes O 100% 100% 100% (60% bc/coh) 6L PPYes O 100% 100% 100% (90% bc/coh) 6M TPO Yes C 100% 100% 100% 6N PP YesC 100% 100% 100% (80% bc/coh) Comparative 6O TPO Yes None 100% 100% 100%Comparative 6P PP Yes None  90% 100% 100% Comparative 6Q TPO Yes None100%  90% 100% Comparative 6R PP Yes None  90%  40% 100% Comparative 6STPO No O 100% 100% 100% Comparative 6T PP No O 100% 100% 100% 6U TPO YesO 100% 100% 100% 6V PP Yes O 100% 100% 100% ²⁸24 hour coating adhesionwas measured as described above in Table 1. ²⁹7 days coating adhesionwas evaluated as described above in Table 2. ³⁰10 day humidity coatingadhesion was evaluated as described above in Table 2. ³¹Ad Pro Spray Owas prepared by reducing the composition prepared in Example B to 5%solids using xylene. ³²Ad Pro Spray B was prepared and applied asdescribed in Table 1 above. ³³Ad Pro Spray C was prepared and applied asdescribed in Table 1 above.

Example 7

Thermoplastic polyolefin (“TPO”) and polypropylene (“PP”) substrateswere subjected coating processes wherein an adhesion promoting agent wasapplied to the substrate. First, the surface to be painted was wipedwith a Scuff Sponge saturated with a cleaning composition prepared asdescribed in Example G. After rinsing with water and drying, the surfaceto be painted was wiped with a composition comprising an adhesionpromoting agent. The compositions and preparation of the wipes isdescribed in Table 3 and identified as “Ad Pro Wipe”. As is apparent inTable 7, in certain Comparative Examples, this wiping step was omitted.After allowing to dry, the surface to be painted was sprayed with acomposition comprising an adhesion promoting agent. The variouscompositions used are described in Table 7 and identified as “Ad ProSpray”. These compositions were sprayed onto the area of the substrateto be painted using a HVLP hand spray gun. As is apparent in Table 7, incertain Comparative Examples, this spraying step was omitted. Afterdrying, the substrate was painted with BC3964 basecoat and D893 low VOCclearcoat, in accordance with the manufacturer's instructions. Resultsare reported in Table 7.

TABLE 7 Ad Ad Pro Adhesion Adhesion 7 Example Substrate Pro Wipe TypeSpray Type 24 hr³⁴ day³⁵ Comparative 7A TPO P³⁶ None 100% 100%Comparative 7B PP P None  10%  80% Comparative 7C TPO None C⁴⁰  88% 100%Comparative 7D PP None C  0%  0% 7E TPO P C 100% 100% 7F PP P C  88%100% Comparative 7G TPO Q³⁷ None 100% 100% Comparative 7H PP Q None  75%100% Comparative 7I TPO None B⁴¹ 100% 100% Comparative 7J PP None B  0% 75% 7K TPO Q B 100% 100% 7L PP Q B 100% 100% Comparative 7M TPO R³⁸None 100% 100% Comparative 7N PP R None  95% 100% Comparative 7O TPONone U⁴² 100% 100% Comparative 7P PP None U  0%  65% 7Q TPO R U 100%100% 7R PP R U 100% 100% Comparative 7S TPO S³⁹ None 100% 100%Comparative 7T PP S None 100% 100% Comparative 7U TPO None V⁴³ 100% 100%Comparative 7V PP None V  0%  15% 7W TPO S V 100% 100% 7X PP S V 100%100% ³⁴24 hour coating adhesion was measured as described above inTable 1. ³⁵7 days coating adhesion was evaluated as described above inTable 2. ³⁶Ad Pro Wipe Type P was prepared by reducing DPX 801 to 1%solids using P273-1050. The wipe was prepared by pouring thatcomposition onto a Kimtech ® Precision Wipe and allowing the excess todrip off of the wipe. ³⁷Ad Pro Wipe Type Q was prepared by reducing thecomposition prepared in Example A to 1% solids using P273-1050. The wipewas prepared by pouring that composition onto a Kimtech ® Precision Wipeand allowing the excess to drip off of the wipe. ³⁸Ad Pro Wipe Type Rwas prepared by reducing the composition prepared in Example C to 1%solids using P273-1050. The wipe was prepared by pouring thatcomposition onto a Kimtech ® Precision Wipe and allowing the excess todrip off of the wipe. ³⁹Ad Pro Wipe Type S was prepared by reducing thecomposition prepared in Example D to 1% solids using P273-1050. The wipewas prepared by pouring that composition onto a Kimtech ® Precision Wipeand allowing the excess to drip off of the wipe. ⁴⁰Ad Pro Spray Type Cwas prepared and applied as described in Table 1 above. ⁴¹Ad Pro SprayType B was prepared and applied as described in Table 1 above. ⁴²Ad ProSpray Type U was prepared by reducing the composition prepared inExample C to 5% solids using xylene. ⁴³Ad Pro Spray Type V was preparedby reducing the composition prepared in Example D to 5% solids usingxylene.

As is apparent from the foregoing, while refinishing processes thatapply an adhesion promoting agent only once during the refinish processoften result in coatings that have adequate, or even excellent, adhesionto a plastic substrate, the methods and systems of the present inventioncan provide consistently excellent adhesion results. Indeed, it isanticipated that the methods and systems of the present invention canresult in coatings with excellent adhesion over plastic substrates moreconsistently than processes wherein an adhesion promoting agent isapplied only once, particularly in an automobile body shop setting.

It will be readily appreciated by those skilled in the art thatmodifications may be made to the invention without departing from theconcepts disclosed in the foregoing description. Such modifications areto be considered as included within the following claims unless theclaims, by their language, expressly state otherwise. Accordingly, theparticular embodiments described in detail herein are illustrative onlyand are not limiting to the scope of the invention which is to be giventhe full breadth of the appended claims and any and all equivalentsthereof.

1-17. (canceled)
 18. A method for coating an article comprising aplastic substrate, the method comprising the steps of: a. applying afirst composition comprising an adhesion promoting agent to at least aportion of the substrate; b. applying a second composition comprising anadhesion promoting agent over at least a portion of the compositionapplied in step (a); and c. applying a protective and decorative coatingsystem over at least a portion of the compositions applied in steps (a)and (b), wherein the first composition and the second composition aredifferent and wherein at least one of the first and second compositionsis applied to the substrate by wiping and wherein the adhesion promotingagent comprise a halogenated polyolefin that is modified by grafting acompatibilizing material onto the polyolefin.
 19. The method of claim18, wherein the adhesion promoting agent of the first composition is thesame as the adhesion promoting agent of the second composition.
 20. Themethod of claim 18, wherein the adhesion promoting agent of the firstand/or second composition comprises a halogenated polyolefin, ahalogenated polyolefin that is modified by grafting a compatibilizingmaterial onto the polyolefin, or a mixture thereof.
 21. (canceled) 22.The method of claim 21, wherein the halogenated polyolefin that ismodified by grafting a compatibilizing material onto the polyolefincomprises a chlorinated polyolefin having an acrylic monomer graftedthereon.
 23. The method of claim 18, wherein the adhesion promotingagent comprises 1 up to 10 percent by weight of the first composition.24. The method of claim 18, wherein the first composition furthercomprises an organic solvent.
 25. The method of claim 24, wherein thefirst composition further comprises an anti-static agent.
 26. The methodof claim 18, wherein the first composition comprises an emulsionprepared by introducing an organic component comprising an adhesionpromoting agent into an aqueous medium.
 27. The method of claim 18,wherein the first composition is applied to the substrate by wiping thesubstrate with an absorbent fibrous material loaded with the compositioncomprising an adhesion promoting agent.
 28. The method of claim 18further comprising the step of cleaning the substrate before applyingthe first composition.
 29. The method of claim 28, wherein the cleaningstep comprises contacting the substrate with an abrasive material havinga cleaning composition contained therein.
 30. The method of claim 18,wherein the adhesion promoting agent comprises 1 up to 50 percent byweight of the second composition.
 31. The method of claim 18, whereinone of the first composition and the second composition is applied byspraying.
 32. The method of claim 31, wherein one of the firstcomposition and the second composition is in the form of an aerosol. 33.A method for coating an article comprising a plastic substrate, themethod comprising the steps of: a. applying a composition comprising anadhesion promoting agent to at least a portion of a plastic substrate bya first application technique; and b. applying a protective anddecorative coating system over at least a portion of the compositionapplied in step (a), wherein the protective and decorative coatingsystem comprises a coating layer deposited from a coating compositionthat comprises an (i) adhesion promoting agent comprising a halogenatedpolyolefin, and (ii) a resin that is compatible with the adhesionpromoting agent, and wherein the coating layer is deposited by anapplication technique that is the same as or different from the firstapplication technique.
 34. The method of claim 33, wherein, prior tostep (b), a composition comprising an adhesion promoting agent isapplied over at least a portion of the composition applied in step (a)by a second application technique that is different from the firstapplication technique.
 35. The method of claim 34, wherein the adhesionpromoting agent present in the composition applied by the secondapplication technique is the same as the adhesion promoting agentpresent in the composition applied by the first application technique.36. The method of claim 33, wherein the protective and decorativecoating system comprises a coating layer deposited from a coatingcomposition that comprises an adhesion promoting agent comprising ahalogenated polyolefin that is modified by grafting a compatibilizingmaterial onto the polyolefin.
 37. The method of claim 36, wherein thehalogenated polyolefin that is modified by grafting a compatibilizingmaterial onto the polyolefin comprises a chlorinated polyolefin havingan acrylic monomer grafted thereon.
 38. The method of claim 33, whereinthe resin comprises a thermosetting or thermoplastic polymericcomposition.
 39. The method of claim 38, wherein the resin comprises apolymeric composition selected from the group consisting of acrylicpolymers, polyesters, polyurethanes, polyureas, and mixtures thereof.40. The method of claim 33, wherein the adhesion promoting agentcomprises 1 up to 10 percent by weight of the composition applied by thefirst application technique.
 41. The method of claim 33, wherein thefirst application technique comprises wiping.
 42. The method of claim41, wherein the first application technique comprises wiping thesubstrate with an absorbent fibrous material loaded with the compositioncomprising an adhesion promoting agent.
 43. The method of claim 33further comprising the step of cleaning the substrate before applying acomposition comprising an adhesion promoting agent.
 44. The method ofclaim 43, wherein the cleaning step comprises contacting the substratewith an abrasive material having a cleaning composition containedtherein.
 45. The method of claim 34, wherein the adhesion promotingagent comprises 1 up to 50 percent by weight of the composition appliedby the second application technique.
 46. The method of claim 34, whereinthe composition applied by the second application technique is differentthan the composition applied by the first application technique.
 47. Themethod of claim 34, wherein the second application technique comprisesspraying.
 48. The method of claim 34, wherein the composition applied bythe second application technique is in the form of an aerosol.
 49. Themethod of claim 33, wherein the protective and decorative coating systemcomprises a coating layer deposited from a coating composition thatcomprises an adhesion promoting agent comprising a halogenatedpolyolefin, wherein the adhesion promoting agent comprises 0.1 to 20.0percent by weight of the composition.
 50. The method of claim 49,wherein the protective and decorative coating system comprises a coatinglayer deposited from a coating composition that comprises an adhesionpromoting agent comprising a halogenated polyolefin, wherein theadhesion promoting agent comprises 1.0 to 5.0 percent by weight of thecomposition.
 51. A system for coating an article comprising a plasticsubstrate comprising: a. a cleaning tool; b. means for applying acomposition comprising an adhesion promoting agent to at least a portionof the substrate by a first application technique; c. means for applyinga composition comprising an adhesion promoting agent to at least aportion of the substrate by a second application technique that isdifferent from the first application technique; and d. means forapplying a protective and decorative coating system to at least aportion of the substrate.
 52. The system of claim 51, wherein thecleaning tool and the means for applying a composition comprising anadhesion promoting agent to at least a portion of the substrate by afirst application technique are present in the form of a kit.
 53. Thesystem of claim 51, wherein the kit further comprises the means forapplying a composition comprising an adhesion promoting agent to atleast a portion of the substrate by a second application technique. 54.The system of claim 51, wherein the adhesion promoting agent present inthe composition applied by the second application technique is the sameas the adhesion promoting agent present in the composition applied bythe first application technique.
 55. The system of claim 51, wherein theadhesion promoting agent present in the composition applied by the firstapplication technique and/or the composition applied by the secondapplication technique comprises a halogenated polyolefin, a halogenatedpolyolefin that is modified by grafting a compatibilizing material ontothe polyolefin, or a mixture thereof.
 56. The system of claim 51,wherein the adhesion promoting agent present in the composition appliedby the first application technique and/or the composition applied by thesecond application technique comprises a halogenated polyolefin that ismodified by grafting a compatibilizing material onto the polyolefin. 57.The system of claim 56, wherein the halogenated polyolefin that ismodified by grafting a compatibilizing material onto the polyolefincomprises a chlorinated polyolefin having an acrylic monomer graftedthereon.
 58. The system of claim 51, wherein the adhesion promotingagent comprises 1 up to 10 percent by weight of the composition appliedby the first application technique.
 59. The system of claim 51, whereinthe composition applied by the first application technique comprises anemulsion prepared by introducing an organic component comprising anadhesion promoting agent into an aqueous medium.
 60. The system of claim51, wherein the means for applying a composition comprising an adhesionpromoting agent to at least a portion of the substrate by a firstapplication technique comprises an absorbent fibrous material loadedwith the composition comprising an adhesion promoting agent.
 61. Thesystem of claim 51 wherein the cleaning tool comprises an abrasivematerial having a cleaning composition contained therein.
 62. The systemof claim 51, wherein the adhesion promoting agent comprises 1 up to 50percent by weight of the composition applied by the second applicationtechnique.
 63. The system of claim 51, wherein the composition appliedby the second application technique is different than the compositionapplied by the first application technique.
 64. The system of claim 63,wherein the composition applied by the second application technique isin the form of an aerosol.